Polyurethane
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Polyurethane (; often abbreviated PUR and PU) is a class of
polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...
s composed of organic units joined by
carbamate In organic chemistry, a carbamate is a category of organic compounds with the general Chemical formula, formula and Chemical structure, structure , which are formally Derivative (chemistry), derived from carbamic acid (). The term includes orga ...
(urethane) links. In contrast to other common polymers such as
polyethylene Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging (plastic bags, plastic films, geomembranes and containers including bott ...
and
polystyrene Polystyrene (PS) is a synthetic polymer made from monomers of the aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. It is an inexpensive resin per unit weight. It i ...
, polyurethane term does not refer to the single type of polymer but a group of polymers. Unlike
polyethylene Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging (plastic bags, plastic films, geomembranes and containers including bott ...
and
polystyrene Polystyrene (PS) is a synthetic polymer made from monomers of the aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. It is an inexpensive resin per unit weight. It i ...
, polyurethanes can be produced from a wide range of starting materials resulting in various polymers within the same group. This chemical variety produces polyurethanes with different chemical structures leading to many different applications. These include rigid and flexible
foam Foams are two-phase materials science, material systems where a gas is dispersed in a second, non-gaseous material, specifically, in which gas cells are enclosed by a distinct liquid or solid material. Note, this source focuses only on liquid ...
s, and coatings, adhesives, electrical potting compounds, and fibers such as
spandex Spandex, Lycra, or elastane is a synthetic fiber known for its exceptional elasticity. It is a polyether- polyurea copolymer that was invented in 1958 by chemist Joseph Shivers at DuPont. Name The name ''spandex'', which is an anagram of t ...
and
polyurethane laminate Polyurethane laminate (PUL, thermal stretch, fuzzy rubber) is a compound fabric made by laminating a cloth fabric to one or both sides of a thin film of polyurethane. Polyurethane laminated fabrics have a wide range of applications in medical, au ...
(PUL). Foams are the largest application accounting for 67% of all polyurethane produced in 2016. A polyurethane is typically produced by reacting a polymeric
isocyanate In organic chemistry, isocyanate is the functional group with the formula . Organic compounds that contain an isocyanate group are referred to as isocyanates. An organic compound with two isocyanate groups is known as a diisocyanate. Diisocyan ...
with a
polyol In organic chemistry, a polyol is an organic compound containing multiple hydroxyl groups (). The term "polyol" can have slightly different meanings depending on whether it is used in food science or polymer chemistry. Polyols containing two, th ...
. Since a polyurethane contains two types of monomers, which polymerize one after the other, they are classed as alternating copolymers. Both the isocyanates and polyols used to make a polyurethane contain two or more
functional group In organic chemistry, a functional group is any substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions r ...
s per molecule. Global production in 2019 was 25 million metric tonnes, accounting for about 6% of all polymers produced in that year.


History

Otto Bayer Otto Bayer (4 November 1902 – 1 August 1982) was a German industrial chemist at IG Farben who was head of the research group that in 1937 discovered the polyaddition for the synthesis of polyurethanes out of poly-isocyanate and polyol. Ba ...
and his coworkers at
IG Farben I. G. Farbenindustrie AG, commonly known as IG Farben, was a German Chemical industry, chemical and Pharmaceutical industry, pharmaceutical conglomerate (company), conglomerate. It was formed on December 2, 1925 from a merger of six chemical co ...
in Leverkusen, Germany, first made polyurethanes in 1937. The new polymers had some advantages over existing plastics that were made by polymerizing olefins or by
polycondensation In polymer chemistry, condensation polymers are any kind of polymers whose process of polymerization involves a condensation reaction (i.e. a small molecule, such as water or methanol, is produced as a byproduct). Natural proteins as well as s ...
, and were not covered by patents obtained by
Wallace Carothers Wallace Hume Carothers (; April 27, 1896 – April 29, 1937) was an American chemist, inventor, and the leader of organic chemistry at DuPont, who was credited with the invention of nylon. Carothers was a group leader at the DuPont Experimen ...
on
polyester Polyester is a category of polymers that contain one or two ester linkages in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include some natura ...
s. Early work focused on the production of fibers and flexible foams and PUs were applied on a limited scale as aircraft coating during
World War II World War II or the Second World War (1 September 1939 – 2 September 1945) was a World war, global conflict between two coalitions: the Allies of World War II, Allies and the Axis powers. World War II by country, Nearly all of the wo ...
.
Polyisocyanate In organic chemistry, isocyanate is the functional group with the formula . Organic compounds that contain an isocyanate group are referred to as isocyanates. An organic compound with two isocyanate groups is known as a diisocyanate. Diisocyan ...
s became commercially available in 1952, and production of flexible polyurethane foam began in 1954 by combining
toluene diisocyanate Toluene diisocyanate (TDI) is an organic compound with the formula CH3C6H3(NCO)2. Two of the six possible isomers are commercially important: 2,4-TDI (CAS: 584-84-9) and 2,6-TDI (CAS: 91-08-7). 2,4-TDI is produced in the pure state, but TDI is oft ...
(TDI) and polyester polyols. These materials were also used to produce rigid foams, gum rubber, and
elastomer An elastomer is a polymer with viscoelasticity (i.e. both viscosity and elasticity) and with weak intermolecular forces, generally low Young's modulus (E) and high failure strain compared with other materials. The term, a portmanteau of ''ela ...
s. Linear fibers were produced from
hexamethylene diisocyanate Hexamethylene diisocyanate (HDI) is the organic compound with the formula (CH2)6(NCO)2. It is classified as an diisocyanate. It is a colorless liquid. It has sometimes been called HMDI but this not usually done to avoid confusion with Hydrogenate ...
(HDI) and 1,4-Butanediol (BDO).
DuPont Dupont, DuPont, Du Pont, duPont, or du Pont may refer to: People * Dupont (surname) Dupont, also spelled as DuPont, duPont, Du Pont, or du Pont is a French surname meaning "of the bridge", historically indicating that the holder of the surname re ...
introduced polyethers, specifically
poly(tetramethylene ether) glycol Polytetrahydrofuran, also called poly(tetramethylene ether) glycol or poly(tetramethylene oxide), is a collection of chemical compounds with formula or HO((CH2)4O-)''n''-H. The material is a mixture of polyether diols terminated with alcohol gr ...
, in 1956.
BASF BASF SE (), an initialism of its original name , is a European Multinational corporation, multinational company and the List of largest chemical producers, largest chemical producer in the world. Its headquarters are located in Ludwigshafen, Ge ...
and
Dow Chemical The Dow Chemical Company is an American multinational corporation headquartered in Midland, Michigan, United States. The company was among the three largest chemical producers in the world in 2021. It is the operating subsidiary of Dow Inc., ...
introduced polyalkylene glycols in 1957. Polyether polyols were cheaper, easier to handle and more water-resistant than polyester polyols.
Union Carbide Union Carbide Corporation (UCC) is an American chemical company headquartered in Seadrift, Texas. It has been a wholly owned subsidiary of Dow Chemical Company since 2001. Union Carbide produces chemicals and polymers that undergo one or more f ...
and
Mobay Mobay Chemical Corporation, based in Pittsburgh, Pennsylvania, was a joint venture of Monsanto Company and Bayer to market polyurethanes in the United States. Founded in 1954, Bayer bought out Monsanto's shares in the company in the 1970s. Moba ...
, a U.S.
Monsanto The Monsanto Company () was an American agrochemical and agricultural biotechnology corporation founded in 1901 and headquartered in Creve Coeur, Missouri. Monsanto's best-known product is Roundup, a glyphosate-based herbicide, developed ...
/
Bayer Bayer AG (English: , commonly pronounced ; ) is a German multinational pharmaceutical and biotechnology company and is one of the largest pharmaceutical companies and biomedical companies in the world. Headquartered in Leverkusen, Bayer' ...
joint venture, also began making polyurethane chemicals. In 1960 more than 45,000 metric tons of flexible polyurethane foams were produced. The availability of chlorofluoroalkane blowing agents, inexpensive polyether polyols, and
methylene diphenyl diisocyanate Methylene diphenyl diisocyanate (MDI) is an aromaticity, aromatic diisocyanate. Three isomers are common, varying by the positions of the isocyanate groups around the rings: 2,2′-MDI, 2,4′-MDI, and 4,4′-MDI. The 4,4′ isomer is most widel ...
(MDI) allowed polyurethane rigid foams to be used as high-performance insulation materials. In 1967, urethane-modified polyisocyanurate rigid foams were introduced, offering even better thermal stability and
flammability A combustible material is a material that can burn (i.e., sustain a flame) in air under certain conditions. A material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort a ...
resistance. During the 1960s, automotive interior safety components, such as instrument and door panels, were produced by back-filling
thermoplastic A thermoplastic, or thermosoftening plastic, is any plastic polymer material that becomes pliable or moldable at a certain elevated temperature and solidifies upon cooling. Most thermoplastics have a high molecular weight. The polymer chains as ...
skins with semi-rigid foam. In 1969, Bayer exhibited an all-plastic car in
Düsseldorf Düsseldorf is the capital city of North Rhine-Westphalia, the most populous state of Germany. It is the second-largest city in the state after Cologne and the List of cities in Germany with more than 100,000 inhabitants, seventh-largest city ...
, Germany. Parts of this car, such as the
fascia A fascia (; : fasciae or fascias; adjective fascial; ) is a generic term for macroscopic membranous bodily structures. Fasciae are classified as superficial, visceral or deep, and further designated according to their anatomical location. ...
and body panels, were manufactured using a new process called
reaction injection molding Reaction injection molding (RIM) is similar to injection molding except thermosetting polymers are used, which requires a curing reaction to occur within the mold. Common items made via RIM include automotive bumpers, air spoilers, and fe ...
(RIM), in which the reactants were mixed and then injected into a mold. The addition of fillers, such as milled glass,
mica Micas ( ) are a group of silicate minerals whose outstanding physical characteristic is that individual mica crystals can easily be split into fragile elastic plates. This characteristic is described as ''perfect basal cleavage''. Mica is co ...
, and processed mineral fibers, gave rise to reinforced RIM (RRIM), which provided improvements in flexural modulus (stiffness), reduction in coefficient of
thermal expansion Thermal expansion is the tendency of matter to increase in length, area, or volume, changing its size and density, in response to an increase in temperature (usually excluding phase transitions). Substances usually contract with decreasing temp ...
and better thermal stability. This technology was used to make the first plastic-body automobile in the United States, the
Pontiac Fiero The Pontiac Fiero is a Rear mid-engine, rear-wheel-drive layout, rear mid-engine, light sports car manufactured and marketed by Pontiac (automobile), Pontiac for model years 1984 – 1988. Intended as an economical commuter car with modest perf ...
, in 1983. Further increases in stiffness were obtained by incorporating pre-placed glass mats into the RIM mold cavity, also known broadly as resin injection molding, or structural RIM. Starting in the early 1980s, water-blown microcellular flexible foams were used to mold gaskets for automotive panels and air-filter seals, replacing PVC polymers. Polyurethane foams are used in many automotive applications including seating, head and arm rests, and headliners. Polyurethane foam (including foam rubber) is sometimes made using small amounts of
blowing agent A blowing agent is a substance which is capable of producing a cellular structure via a foaming process in a variety of materials that undergo hardening or phase transition, such as polymers, plastics, and metals. They are typically applied whe ...
s to give less dense foam, better cushioning/energy absorption or thermal insulation. In the early 1990s, because of their impact on
ozone depletion Ozone depletion consists of two related events observed since the late 1970s: a lowered total amount of ozone in Earth, Earth's upper atmosphere, and a much larger springtime decrease in stratospheric ozone (the ozone layer) around Earth's polar ...
, the
Montreal Protocol The Montreal Protocol on Substances That Deplete the Ozone Layer is an international treaty designed to protect the ozone layer by phasing out the production of numerous substances that are responsible for ozone depletion. It was agreed on 16 ...
restricted the use of many
chlorine Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...
-containing blowing agents, such as
trichlorofluoromethane Trichlorofluoromethane, also called freon-11, CFC-11, or R-11, is a chlorofluorocarbon (CFC). It is a colorless, faintly ethereal, and sweetish-smelling liquid that boils around room temperature. CFC-11 is a Class 1 ozone-depleting substance w ...
(CFC-11). By the late 1990s, blowing agents such as
carbon dioxide Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...
,
pentane Pentane is an organic compound with the chemical formula, formula C5H12—that is, an alkane with five carbon atoms. The term may refer to any of three structural isomerism, structural isomers, or to a mixture of them: in the IUPAC nomenclature, h ...
,
1,1,1,2-tetrafluoroethane 1,1,1,2-Tetrafluoroethane (also known as norflurane ( INN), R-134a, Klea 134a, Freon 134a, Forane 134a, Genetron 134a, Green Gas, Florasol 134a, Suva 134a, HFA-134a, or HFC-134a) is a hydrofluorocarbon (HFC) and haloalkane refrigerant with th ...
(HFC-134a) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) were widely used in North America and the EU, although chlorinated blowing agents remained in use in many developing countries. Later, HFC-134a was also banned due to high ODP and GWP readings, and HFC-141B was introduced in early 2000s as an alternate blowing agent in developing nations.


Chemistry

Polyurethanes are produced by reacting di
isocyanate In organic chemistry, isocyanate is the functional group with the formula . Organic compounds that contain an isocyanate group are referred to as isocyanates. An organic compound with two isocyanate groups is known as a diisocyanate. Diisocyan ...
s with
polyol In organic chemistry, a polyol is an organic compound containing multiple hydroxyl groups (). The term "polyol" can have slightly different meanings depending on whether it is used in food science or polymer chemistry. Polyols containing two, th ...
s,''n'' â‰¥ 2 often in the presence of a
catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
, or upon exposure to ultraviolet radiation. Common catalysts include tertiary
amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
s, such as DABCO, DMDEE, or
metallic soap A metallic soap is a metallic salt of a fatty acid. Theoretically, soaps can be made of any metal, although not all enjoy practical uses. Varying the metal can strongly affect the properties of the compound, particularly its solubility. Alkali, ...
s, such as dibutyltin dilaurate. The
stoichiometry Stoichiometry () is the relationships between the masses of reactants and Product (chemistry), products before, during, and following chemical reactions. Stoichiometry is based on the law of conservation of mass; the total mass of reactants must ...
of the starting materials must be carefully controlled as excess isocyanate can trimerise, leading to the formation of rigid polyisocyanurates. The polymer usually has a highly
crosslink In chemistry and biology, a cross-link is a bond or a short sequence of bonds that links one polymer chain to another. These links may take the form of covalent bonds or ionic bonds and the polymers can be either synthetic polymers or natural ...
ed molecular structure, resulting in a thermosetting material which does not melt on heating; although some
thermoplastic polyurethane Thermoplastic polyurethane (TPU) is any of the polyurethane polymers that are thermoplastic; that is, they become pliable when heated and harden when cooled. This is in contrast to most polyurethanes, which are thermosets, hardening irreversibly. ...
s are also produced. The most common application of polyurethane is as solid
foam Foams are two-phase materials science, material systems where a gas is dispersed in a second, non-gaseous material, specifically, in which gas cells are enclosed by a distinct liquid or solid material. Note, this source focuses only on liquid ...
s, which requires the presence of a gas, or
blowing agent A blowing agent is a substance which is capable of producing a cellular structure via a foaming process in a variety of materials that undergo hardening or phase transition, such as polymers, plastics, and metals. They are typically applied whe ...
, during the polymerization step. This is commonly achieved by adding small amounts of water, which reacts with isocyanates to form CO2 gas and an
amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
, via an unstable
carbamic acid Carbamic acid, which might also be called aminoformic acid or aminocarboxylic acid, is the chemical compound with the formula . It can be obtained by the reaction of ammonia and carbon dioxide at very low temperatures, which also yields ammoni ...
group. The amine produced can also react with isocyanates to form
urea Urea, also called carbamide (because it is a diamide of carbonic acid), is an organic compound with chemical formula . This amide has two Amine, amino groups (–) joined by a carbonyl functional group (–C(=O)–). It is thus the simplest am ...
groups, and as such the polymer will contain both these and urethane linkers. The urea is not very soluble in the reaction mixture and tends to form separate "hard segment" phases consisting mostly of polyurea. The concentration and organization of these polyurea phases can have a significant impact on the properties of the foam. The type of foam produced can be controlled by regulating the amount of blowing agent and also by the addition of various
surfactant Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. The word ''surfactant'' is a Blend word, blend of "surface-active agent", coined in ...
s which change the
rheology Rheology (; ) is the study of the flow of matter, primarily in a fluid (liquid or gas) state but also as "soft solids" or solids under conditions in which they respond with plastic flow rather than deforming elastically in response to an applie ...
of the polymerising mixture. Foams can be either "closed-cell", where most of the original bubbles or cells remain intact, or "open-cell", where the bubbles have broken but the edges of the bubbles are stiff enough to retain their shape, in extreme cases reticulated foams can be formed. Open-cell foams feel soft and allow air to flow through, so they are comfortable when used in seat cushions or
mattresses A mattress is a large, usually rectangular pad for supporting a person Lying (position), lying down, especially for sleeping. It is designed to be used as a bed, or on a bed frame as part of a bed. Mattresses may consist of a Quilting, quilted o ...
. Closed-cell foams are used as rigid
thermal insulation Thermal insulation is the reduction of heat transfer (i.e., the transfer of thermal energy between objects of differing temperature) between objects in thermal contact or in range of radiative influence. Thermal insulation can be achieved with s ...
. High-density microcellular foams can be formed without the addition of blowing agents by mechanically frothing the polyol prior to use. These are tough elastomeric materials used in covering car
steering wheel A steering wheel (also called a driving wheel, a hand wheel, or simply wheel) is a type of steering control in vehicles. Steering wheels are used in most modern land vehicles, including all mass-production automobiles, buses, light and hea ...
s or shoe soles. The properties of a polyurethane are greatly influenced by the types of isocyanates and polyols used to make it. Long, flexible segments, contributed by the polyol, give soft,
elastic Elastic is a word often used to describe or identify certain types of elastomer, Elastic (notion), elastic used in garments or stretch fabric, stretchable fabrics. Elastic may also refer to: Alternative name * Rubber band, ring-shaped band of rub ...
polymer. High amounts of crosslinking give tough or rigid polymers. Long chains and low crosslinking give a polymer that is very stretchy, short chains with many crosslinks produce a hard polymer while long chains and intermediate crosslinking give a polymer useful for making foam. The choices available for the isocyanates and polyols, in addition to other additives and processing conditions allow polyurethanes to have the very wide range of properties that make them such widely used polymers.


Raw materials

The main ingredients to make a polyurethane are di- and tri-
isocyanates In organic chemistry, isocyanate is the functional group with the formula . Organic compounds that contain an isocyanate group are referred to as isocyanates. An organic compound with two isocyanate groups is known as a diisocyanate. Diisocyan ...
and
polyols In organic chemistry, a polyol is an organic compound containing multiple hydroxyl groups (). The term "polyol" can have slightly different meanings depending on whether it is used in food science or polymer chemistry. Polyols containing two, thre ...
. Other materials are added to aid processing the polymer or to modify the properties of the polymer. PU foam formulation sometimes have water added too.


Isocyanates

Isocyanates used to make polyurethane have two or more isocyanate groups on each molecule. The most commonly used isocyanates are the
aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...
diisocyanates,
toluene diisocyanate Toluene diisocyanate (TDI) is an organic compound with the formula CH3C6H3(NCO)2. Two of the six possible isomers are commercially important: 2,4-TDI (CAS: 584-84-9) and 2,6-TDI (CAS: 91-08-7). 2,4-TDI is produced in the pure state, but TDI is oft ...
(TDI) and
methylene diphenyl diisocyanate Methylene diphenyl diisocyanate (MDI) is an aromaticity, aromatic diisocyanate. Three isomers are common, varying by the positions of the isocyanate groups around the rings: 2,2′-MDI, 2,4′-MDI, and 4,4′-MDI. The 4,4′ isomer is most widel ...
, (MDI). These aromatic isocyanates are more reactive than
aliphatic In organic chemistry, hydrocarbons ( compounds composed solely of carbon and hydrogen) are divided into two classes: aromatic compounds and aliphatic compounds (; G. ''aleiphar'', fat, oil). Aliphatic compounds can be saturated (in which all ...
isocyanates. TDI and MDI are generally less expensive and more reactive than other isocyanates. Industrial grade TDI and MDI are mixtures of isomers and MDI often contains polymeric materials. They are used to make flexible foam (for example slabstock foam for mattresses or molded foams for car seats), rigid foam (for example insulating foam in refrigerators) elastomers (shoe soles, for example), and so on. The isocyanates may be modified by partially reacting them with polyols or introducing some other materials to reduce volatility (and hence toxicity) of the isocyanates, decrease their freezing points to make handling easier or to improve the properties of the final polymers. Aliphatic and cycloaliphatic isocyanates are used in smaller quantities, most often in coatings and other applications where color and transparency are important since polyurethanes made with aromatic isocyanates tend to darken on exposure to light. The most important aliphatic and cycloaliphatic isocyanates are 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (
isophorone diisocyanate Isophorone diisocyanate (IPDI) is an organic compound in the class known as isocyanates. More specifically, it is an Aliphatic compound, aliphatic diisocyanate. It is produced in relatively small quantities, accounting for (with hexamethylene diis ...
, IPDI), and 4,4′-diisocyanato dicyclohexylmethane (H12MDI or hydrogenated MDI). Other more specialized isocyanates include Tetramethylxylylene diisocyanate (TMXDI).


Polyols

Polyols In organic chemistry, a polyol is an organic compound containing multiple hydroxyl groups (). The term "polyol" can have slightly different meanings depending on whether it is used in food science or polymer chemistry. Polyols containing two, thre ...
are polymers in their own right and have on average two or more hydroxyl groups per molecule. They can be converted to polyether polyols by co-polymerizing
ethylene oxide Ethylene oxide is an organic compound with the chemical formula, formula . It is a cyclic ether and the simplest epoxide: a three-membered ring (chemistry), ring consisting of one oxygen atom and two carbon atoms. Ethylene oxide is a colorless ...
and
propylene oxide Propylene oxide is an epoxide with the molecular formula C3H6O. This colourless volatile liquid with an odour similar to ether, is produced on a large scale industrially. Its major application is its use for the production of polyether polyols f ...
with a suitable polyol precursor. Polyester polyols are made by the polycondensation of multifunctional
carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an Substituent, R-group. The general formula of a carboxylic acid is often written as or , sometimes as with R referring to an organyl ...
s and polyhydroxyl compounds. They can be further classified according to their end use. Higher molecular weight polyols (molecular weights from 2,000 to 10,000) are used to make more flexible polyurethanes while lower molecular weight polyols make more rigid products. Polyols for flexible applications use low functionality initiators such as dipropylene glycol (''f'' = 2),
glycerine Glycerol () is a simple triol compound. It is a colorless, odorless, sweet-tasting, viscous liquid. The glycerol backbone is found in lipids known as glycerides. It is also widely used as a sweetener in the food industry and as a humectant in ...
(''f'' = 3), or a sorbitol/water solution (''f'' = 2.75). Polyols for rigid applications use higher functionality initiators such as
sucrose Sucrose, a disaccharide, is a sugar composed of glucose and fructose subunits. It is produced naturally in plants and is the main constituent of white sugar. It has the molecular formula . For human consumption, sucrose is extracted and refined ...
(''f'' = 8),
sorbitol Sorbitol (), less commonly known as glucitol (), is a sugar alcohol with a sweet taste which the human body metabolizes slowly. It can be obtained by reduction of glucose, which changes the converted aldehyde group (−CHO) to a primary alco ...
(''f'' = 6), toluenediamine (''f'' = 4), and
Mannich base A Mannich base is a beta- amino-ketone, which is formed in the reaction of an amine, formaldehyde (or an aldehyde) and a carbon acid. The Mannich base is an endproduct in the Mannich reaction, which is nucleophilic addition reaction of a non-en ...
s (''f'' = 4).
Propylene oxide Propylene oxide is an epoxide with the molecular formula C3H6O. This colourless volatile liquid with an odour similar to ether, is produced on a large scale industrially. Its major application is its use for the production of polyether polyols f ...
and/or
ethylene oxide Ethylene oxide is an organic compound with the chemical formula, formula . It is a cyclic ether and the simplest epoxide: a three-membered ring (chemistry), ring consisting of one oxygen atom and two carbon atoms. Ethylene oxide is a colorless ...
is added to the initiators until the desired molecular weight is achieved. The order of addition and the amounts of each oxide affect many polyol properties, such as compatibility, water-solubility, and reactivity. Polyols made with only propylene oxide are terminated with secondary hydroxyl groups and are less reactive than polyols capped with ethylene oxide, which contain primary hydroxyl groups. Incorporating carbon dioxide into the polyol structure is being researched by multiple companies. Graft polyols (also called filled polyols or polymer polyols) contain finely dispersed styrene–acrylonitrile,
acrylonitrile Acrylonitrile is an organic compound with the formula and the structure . It is a colorless, volatile liquid. It has a pungent odor of garlic or onions. Its molecular structure consists of a vinyl group () linked to a nitrile (). It is an im ...
, or polyurea (PHD) polymer solids chemically grafted to a high molecular weight polyether backbone. They are used to increase the load-bearing properties of low-density high-resiliency (HR) foam, as well as add toughness to microcellular foams and cast elastomers. Initiators such as
ethylenediamine Ethylenediamine (abbreviated as en when a ligand) is the organic compound with the formula C2H4(NH2)2. This colorless liquid with an ammonia-like odor is a basic amine. It is a widely used building block in chemical synthesis, with approximately ...
and
triethanolamine Triethanolamine, or TEOA, is an organic compound with the chemical formula . It is a colourless, viscous liquid. It is both a tertiary amine and a triol. A triol is a molecule with three alcohol groups. Approximately 150,000 tonnes were produ ...
are used to make low molecular weight rigid foam polyols that have built-in catalytic activity due to the presence of nitrogen atoms in the backbone. A special class of polyether polyols,
poly(tetramethylene ether) glycol Polytetrahydrofuran, also called poly(tetramethylene ether) glycol or poly(tetramethylene oxide), is a collection of chemical compounds with formula or HO((CH2)4O-)''n''-H. The material is a mixture of polyether diols terminated with alcohol gr ...
s, which are made by polymerizing
tetrahydrofuran Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water- miscible organic liquid with low viscosity. It is ...
, are used in high performance coating, wetting and elastomer applications. Conventional polyester polyols are based on virgin raw materials and are manufactured by the direct polyesterification of high-purity diacids and glycols, such as adipic acid and 1,4-butanediol. Polyester polyols are usually more expensive and more viscous than polyether polyols, but they make polyurethanes with better solvent, abrasion, and cut resistance. Other polyester polyols are based on reclaimed raw materials. They are manufactured by transesterification (
glycolysis Glycolysis is the metabolic pathway that converts glucose () into pyruvic acid, pyruvate and, in most organisms, occurs in the liquid part of cells (the cytosol). The Thermodynamic free energy, free energy released in this process is used to form ...
) of recycled poly(ethyleneterephthalate) (PET) or dimethylterephthalate (DMT) distillation bottoms with glycols such as diethylene glycol. These low molecular weight, aromatic polyester polyols are used in rigid foam, and bring low cost and excellent flammability characteristics to polyisocyanurate (PIR) boardstock and polyurethane spray foam insulation. Specialty polyols include
polycarbonate Polycarbonates (PC) are a group of thermoplastic polymers containing carbonate ester, carbonate groups in their chemical structures. Polycarbonates used in engineering are strong, toughness, tough materials, and some grades are optically transp ...
polyols,
polycaprolactone Polycaprolactone (PCL) is a synthetic, semi-crystalline, biodegradable polyester with a melting point of about 60 Â°C and a glass transition temperature of about −60 Â°C. The most common use of polycaprolactone is in the production ...
polyols,
polybutadiene Polybutadiene utadiene rubber, BRis a synthetic rubber. It offers high elasticity, high resistance to wear, good strength even without fillers, and excellent abrasion resistance when filled and vulcanized. "Polybutadiene" is a collective name fo ...
polyols, and
polysulfide Polysulfides are a class of chemical compounds derived from anionic chains of sulfur atoms. There are two main classes of polysulfides: inorganic and organic. The inorganic polysulfides have the general formula . These anions are the conjugate bas ...
polyols. The materials are used in elastomer, sealant, and adhesive applications that require superior weatherability, and resistance to chemical and environmental attack. Natural oil polyols derived from
castor oil Castor oil is a vegetable oil pressed from castor beans, the seeds of the plant ''Ricinus communis''. The seeds are 40 to 60 percent oil. It is a colourless or pale yellow liquid with a distinct taste and odor. Its boiling point is and its den ...
and other
vegetable oils Vegetable oils, or vegetable fats, are oils extracted from seeds or from other parts of edible plants. Like animal fats, vegetable fats are ''mixtures'' of triglycerides. Soybean oil, grape seed oil, and cocoa butter are examples of seed ...
are used to make elastomers, flexible bunstock, and flexible molded foam. Co-polymerizing chlorotrifluoroethylene or
tetrafluoroethylene Tetrafluoroethylene (TFE) is a fluorocarbon with the chemical formula . It is a colorless gas. Its structure is . It is used primarily in the industrial preparation of fluoropolymers. It is the simplest perfluorinated alkene. It was first repor ...
with vinyl ethers containing hydroxyalkyl vinyl ether produces fluorinated (FEVE) polyols. Two-component fluorinated polyurethanes prepared by reacting FEVE fluorinated polyols with polyisocyanate have been used to make ambient cure paints and coatings. Since fluorinated polyurethanes contain a high percentage of fluorine–carbon bonds, which are the strongest bonds among all chemical bonds, fluorinated polyurethanes exhibit resistance to UV, acids, alkali, salts, chemicals, solvents, weathering, corrosion, fungi and microbial attack. These have been used for high performance coatings and paints.
Phosphorus Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...
-containing polyols are available that become chemically bonded to the polyurethane matrix for the use as
flame retardants Flame retardants are a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an combustion, ignition source and pr ...
. This covalent linkage prevents migration and leaching of the
organophosphorus compound Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbo ...
.


Bio-derived materials

Interest in
sustainable Sustainability is a social goal for people to co-exist on Earth over a long period of time. Definitions of this term are disputed and have varied with literature, context, and time. Sustainability usually has three dimensions (or pillars): env ...
"green" products raised interest in polyols derived from
vegetable oil Vegetable oils, or vegetable fats, are oils extracted from seeds or from other parts of edible plants. Like animal fats, vegetable fats are ''mixtures'' of triglycerides. Soybean oil, grape seed oil, and cocoa butter are examples of seed ...
s, fatty acids, lignin,
sorbitol Sorbitol (), less commonly known as glucitol (), is a sugar alcohol with a sweet taste which the human body metabolizes slowly. It can be obtained by reduction of glucose, which changes the converted aldehyde group (−CHO) to a primary alco ...
, etc. These are mostly contributing to
polyol In organic chemistry, a polyol is an organic compound containing multiple hydroxyl groups (). The term "polyol" can have slightly different meanings depending on whether it is used in food science or polymer chemistry. Polyols containing two, th ...
part. There are attempts made to prepare isocyanate part using bio-derived material. However, as far as commercialization is concern, polyol part is more targeted being easy and required in more quantity than
isocyanate In organic chemistry, isocyanate is the functional group with the formula . Organic compounds that contain an isocyanate group are referred to as isocyanates. An organic compound with two isocyanate groups is known as a diisocyanate. Diisocyan ...
part. Various oils used in the preparation polyols for polyurethanes include
soybean oil Soybean oil (British English: soyabean oil) is a vegetable oil extracted from soybean (''Glycine max'') legumes. It is one of the most widely consumed cooking oils and the second most consumed vegetable oil. As a drying oil, processed soybean oil ...
,
cottonseed oil Cottonseed oil is cooking oil from the seeds of cotton plants of various species, mainly ''Gossypium hirsutum'' and ''Gossypium herbaceum'', that are grown for cotton fiber, animal feed, and oil. cottonseed, Cotton seed has a similar structure to ...
, neem seed oil,
algae Algae ( , ; : alga ) is an informal term for any organisms of a large and diverse group of photosynthesis, photosynthetic organisms that are not plants, and includes species from multiple distinct clades. Such organisms range from unicellular ...
oil, and
castor oil Castor oil is a vegetable oil pressed from castor beans, the seeds of the plant ''Ricinus communis''. The seeds are 40 to 60 percent oil. It is a colourless or pale yellow liquid with a distinct taste and odor. Its boiling point is and its den ...
. Vegetable oils are functionalized in various ways and modified to polyetheramides,
polyether In organic chemistry, ethers are a class of compounds that contain an ether group, a single oxygen atom bonded to two separate carbon atoms, each part of an organyl group (e.g., alkyl or aryl). They have the general formula , where R and R†...
s,
alkyd An alkyd is a polyester resin modified by the addition of fatty acids and other components. Alkyds are derived from polyols and organic acids including dicarboxylic acids or carboxylic acid anhydride and triglyceride oils. The term ''alkyd'' is ...
s, etc. Renewable sources used to prepare polyols may be
fatty acid In chemistry, in particular in biochemistry, a fatty acid is a carboxylic acid with an aliphatic chain, which is either saturated and unsaturated compounds#Organic chemistry, saturated or unsaturated. Most naturally occurring fatty acids have an ...
s or dimer fatty acids. Some biobased and isocyanate-free polyurethanes exploit the reaction between
polyamine A polyamine is an organic compound having two or more amino groups. Alkyl polyamines occur naturally, but some are synthetic. Alkylpolyamines are colorless, hygroscopic, and water soluble. Near neutral pH, they exist as the ammonium derivatives. ...
s and cyclic carbonates to produce polyhydroxyurethanes.


Chain extenders and cross linkers

Chain extenders (''f'' = 2) and cross linkers (''f'' â‰¥ 3) are low molecular weight hydroxyl and amine terminated compounds that play an important role in the polymer morphology of polyurethane fibers, elastomers, adhesives, and certain integral skin and microcellular foams. The elastomeric properties of these materials are derived from the phase separation of the hard and soft copolymer segments of the polymer, such that the urethane hard segment domains serve as cross-links between the amorphous polyether (or polyester) soft segment domains. This phase separation occurs because the mainly nonpolar, low melting soft segments are incompatible with the polar, high melting hard segments. The soft segments, which are formed from high molecular weight polyols, are mobile and are normally present in coiled formation, while the hard segments, which are formed from the isocyanate and chain extenders, are stiff and immobile. As the hard segments are covalently coupled to the soft segments, they inhibit plastic flow of the polymer chains, thus creating elastomeric resiliency. Upon mechanical deformation, a portion of the soft segments are stressed by uncoiling, and the hard segments become aligned in the stress direction. This reorientation of the hard segments and consequent powerful hydrogen bonding contributes to high tensile strength, elongation, and tear resistance values. The choice of chain extender also determines flexural, heat, and chemical resistance properties. The most important chain extenders are
ethylene glycol Ethylene glycol ( IUPAC name: ethane-1,2-diol) is an organic compound (a vicinal diol) with the formula . It is mainly used for two purposes: as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odo ...
, 1,4-butanediol (1,4-BDO or BDO), 1,6-hexanediol, cyclohexane dimethanol and hydroquinone bis(2-hydroxyethyl) ether (HQEE). All of these glycols form polyurethanes that phase separate well and form well defined hard segment domains, and are melt processable. They are all suitable for
thermoplastic polyurethanes Thermoplastic polyurethane (TPU) is any of the polyurethane polymers that are thermoplastic; that is, they become pliable when heated and harden when cooled. This is in contrast to most polyurethanes, which are thermosets, hardening irreversibly ...
with the exception of ethylene glycol, since its derived bis-phenyl urethane undergoes unfavorable degradation at high hard segment levels. Diethanolamine and triethanolamine are used in flex molded foams to build firmness and add catalytic activity. Diethyltoluenediamine is used extensively in RIM, and in polyurethane and polyurea elastomer formulations.


Catalysts

Polyurethane
catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
s can be classified into two broad categories, basic and acidic
amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
.
Tertiary amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
catalysts function by enhancing the nucleophilicity of the diol component. Alkyl tin carboxylates, oxides and mercaptides oxides function as mild Lewis acids in accelerating the formation of polyurethane. As bases, traditional amine catalysts include triethylenediamine (TEDA, also called DABCO, 1,4-diazabicyclo .2.2ctane), dimethylcyclohexylamine (DMCHA),
dimethylethanolamine Dimethylethanolamine (DMAE or DMEA) is an organic compound with the formula . It is bifunctional, containing both a tertiary amine and primary alcohol functional groups. It is a colorless viscous liquid. It is used in skin care products for improv ...
(DMEA), Dimethylaminoethoxyethanol and bis-(2-dimethylaminoethyl)ether, a blowing catalyst also called A-99. A typical Lewis acidic catalyst is dibutyltin dilaurate. The process is highly sensitive to the nature of the catalyst and is also known to be autocatalytic. Another class of catalysts was published in a study in May 2024. In this study, polyurethane synthesis was investigated in the presence of acid catalysts, namely dimethylphosphite (DMHP),
methanesulfonic acid Methanesulfonic acid (MsOH, MSA) or methanesulphonic acid (in British English) is an organosulfuric, colorless liquid with the molecular formula and structure . It is the simplest of the alkylsulfonic acids (). Salts and esters of methanesul ...
(MSA), and
trifluoromethanesulfonic acid Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for este ...
(TFMSA). The thermodynamic profile was examined and described in detail through computational tools, showing that TFMSA had the best catalytic properties. The study aimed to open the door to a new class of catalysts. Factors affecting catalyst selection include balancing three reactions: urethane (polyol+isocyanate, or gel) formation, the urea (water+isocyanate, or "blow") formation, or the isocyanate trimerization reaction (e.g., using potassium acetate, to form isocyanurate rings). A variety of specialized catalysts have been developed.


Surfactants

Surfactants Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. The word ''surfactant'' is a blend of "surface-active agent", coined in 1950. As t ...
are used to modify the characteristics of both foam and non-foam polyurethane polymers. They take the form of polydimethylsiloxane-polyoxyalkylene block copolymers,
silicone In Organosilicon chemistry, organosilicon and polymer chemistry, a silicone or polysiloxane is a polymer composed of repeating units of siloxane (, where R = Organyl group, organic group). They are typically colorless oils or elastomer, rubber ...
oils,
nonylphenol Nonylphenols are a family of closely related organic compounds composed of phenol bearing a 9 carbon-tail. Nonylphenols can come in numerous structures, all of which may be considered alkylphenols. They are used in manufacturing antioxidants, l ...
ethoxylates, and other organic compounds. In foams, they are used to emulsify the liquid components, regulate cell size, and stabilize the cell structure to prevent collapse and sub-surface voids. In non-foam applications they are used as air release and antifoaming agents, as wetting agents, and are used to eliminate surface defects such as pin holes, orange peel, and sink marks.


Production

Polyurethanes are produced by mixing two or more liquid streams. The polyol stream contains catalysts, surfactants,
blowing agent A blowing agent is a substance which is capable of producing a cellular structure via a foaming process in a variety of materials that undergo hardening or phase transition, such as polymers, plastics, and metals. They are typically applied whe ...
s (when making polyurethane foam insulation) and so on. The two components are referred to as a polyurethane system, or simply a system. The isocyanate is commonly referred to in North America as the 'A-side' or just the 'iso'. The blend of polyols and other additives is commonly referred to as the 'B-side' or as the 'poly'. This mixture might also be called a 'resin' or 'resin blend'. In Europe the meanings for 'A-side' and 'B-side' are reversed. Resin blend additives may include chain extenders, cross linkers,
surfactant Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. The word ''surfactant'' is a Blend word, blend of "surface-active agent", coined in ...
s,
flame retardant Flame retardants are a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an combustion, ignition source and pr ...
s,
blowing agent A blowing agent is a substance which is capable of producing a cellular structure via a foaming process in a variety of materials that undergo hardening or phase transition, such as polymers, plastics, and metals. They are typically applied whe ...
s,
pigment A pigment is a powder used to add or alter color or change visual appearance. Pigments are completely or nearly solubility, insoluble and reactivity (chemistry), chemically unreactive in water or another medium; in contrast, dyes are colored sub ...
s, and
fillers In animal feed, a filler is an ingredient added to provide dietary fiber, bulk or some other non-nutritive purpose. Products like corn fiber (corncobs), fruit fibers (pulp), rice bran, and whole grains are possible fillers. Purpose As source ...
. Polyurethane can be made in a variety of densities and hardnesses by varying the isocyanate, polyol or additives.


Health and safety

Fully reacted polyurethane polymer is chemically inert. No exposure limits have been established in the U.S. by OSHA (
Occupational Safety and Health Administration The Occupational Safety and Health Administration (OSHA; ) is a regulatory agency of the United States Department of Labor that originally had federal visitorial powers to inspect and examine workplaces. The United States Congress established ...
) or ACGIH (
American Conference of Governmental Industrial Hygienists The American Conference of Governmental Industrial Hygienists (ACGIH) is a professional association of industrial hygienists and practitioners of related professions, with headquarters in Cincinnati, Ohio. One of its goals is to advance worker pr ...
). It is not regulated by OSHA for carcinogenicity. Polyurethanes are combustible. Decomposition from fire can produce significant amounts of carbon monoxide and
hydrogen cyanide Hydrogen cyanide (formerly known as prussic acid) is a chemical compound with the chemical formula, formula HCN and structural formula . It is a highly toxic and flammable liquid that boiling, boils slightly above room temperature, at . HCN is ...
, in addition to nitrogen oxides, isocyanates, and other toxic products. Due to the flammability of the material, it has to be treated with
flame retardant Flame retardants are a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an combustion, ignition source and pr ...
s (at least in case of furniture), almost all of which are considered harmful. California later issued Technical Bulletin 117 2013 which allowed most polyurethane foam to pass flammability tests without the use of flame retardants. Green Science Policy Institute states: "Although the new standard can be met without flame retardants, it does NOT ban their use. Consumers who wish to reduce household exposure to flame retardants can look for a TB117-2013 tag on furniture, and verify with retailers that products do not contain flame retardants." Liquid resin blends and
isocyanate In organic chemistry, isocyanate is the functional group with the formula . Organic compounds that contain an isocyanate group are referred to as isocyanates. An organic compound with two isocyanate groups is known as a diisocyanate. Diisocyan ...
s may contain hazardous or regulated components. Isocyanates are known skin and respiratory sensitizers. Additionally, amines, glycols, and phosphate present in spray polyurethane foams present risks. Exposure to chemicals that may be emitted during or after application of polyurethane spray foam (such as isocyanates) are harmful to human health and therefore special precautions are required during and after this process. In the United States, additional health and safety information can be found through organizations such as the Polyurethane Manufacturers Association (PMA) and the Center for the Polyurethanes Industry (CPI), as well as from polyurethane system and raw material manufacturers. Regulatory information can be found in the
Code of Federal Regulations In the law of the United States, the ''Code of Federal Regulations'' (''CFR'') is the codification of the general and permanent regulatory law, regulations promulgated by the executive departments and agencies of the federal government of the ...
Title 21 (Food and Drugs) and Title 40 (Protection of the Environment). In Europe, health and safety information is available from ISOPA, the European Diisocyanate and Polyol Producers Association.


Manufacturing

The methods of manufacturing polyurethane finished goods range from small, hand pour piece-part operations to large, high-volume bunstock and boardstock production lines. Regardless of the end-product, the manufacturing principle is the same: to meter the liquid isocyanate and resin blend at a specified stoichiometric ratio, mix them together until a homogeneous blend is obtained, dispense the reacting liquid into a mold or on to a surface, wait until it cures, then demold the finished part.


Dispensing equipment

Although the capital outlay can be high, it is desirable to use a meter-mix or dispense unit for even low-volume production operations that require a steady output of finished parts. Dispense equipment consists of material holding (day) tanks, metering pumps, a mix head, and a control unit. Often, a conditioning or heater–chiller unit is added to control material temperature in order to improve mix efficiency, cure rate, and to reduce process variability. Choice of dispense equipment components depends on shot size, throughput, material characteristics such as
viscosity Viscosity is a measure of a fluid's rate-dependent drag (physics), resistance to a change in shape or to movement of its neighboring portions relative to one another. For liquids, it corresponds to the informal concept of ''thickness''; for e ...
and filler content, and
process control Industrial process control (IPC) or simply process control is a system used in modern manufacturing which uses the principles of control theory and physical industrial control systems to monitor, control and optimize continuous Industrial processe ...
. Material day tanks may be single to hundreds of gallons in size and may be supplied directly from drums, IBCs (
intermediate bulk container Intermediate bulk containers (also known as IBCs, IBC totes, or pallet tanks) are industrial-grade containers engineered for the mass handling, transport, and storage of liquids, partial solids, pastes, granular solids or other fluids. There are ...
s, such as caged IBC totes), or bulk
storage tank Storage tanks are containers that hold liquids or compressed gases. The term can be used for reservoirs (artificial lakes and ponds), and for manufactured containers. The usage of the word "tank" for reservoirs is uncommon in American English ...
s. They may incorporate level sensors, conditioning jackets, and mixers. Pumps can be sized to meter in single grams per second up to hundreds of pounds per minute. They can be rotary, gear, or piston pumps, or can be specially hardened lance pumps to meter liquids containing highly abrasive fillers such as chopped or hammer-milled
glass fiber Glass fiber ( or glass fibre) is a material consisting of numerous extremely fine fibers of glass. Glassmakers throughout history have experimented with glass fibers, but mass manufacture of glass fiber was only made possible with the inventio ...
and
wollastonite Wollastonite is a calcium Silicate minerals, inosilicate mineral (calcium, Casilicon, Sioxygen, O3) that may contain small amounts of iron, magnesium, and manganese substituting for calcium. It is usually white. It forms when impure limestone or D ...
. Image:HighPressureDispenseUnit800x600.png, A high-pressure polyurethane dispense unit, showing control panel, high-pressure pump, integral day tanks, and hydraulic drive unit Image:HighPressureLHeadFront600x800.png, A high-pressure mix head, showing simple controls (front view) Image:HighPressureLHeadRear600x800.png, A high-pressure mix head, showing material supply and hydraulic actuator lines (rear view) The pumps can drive low-pressure (10 to 30 bar, 1 to 3 MPa) or high-pressure (125 to 250 bar, 12.5 to 25.0 MPa) dispense systems. Mix heads can be simple static mix tubes, rotary-element mixers, low-pressure dynamic mixers, or high-pressure hydraulically actuated direct impingement mixers. Control units may have basic on/off and dispense/stop switches, and analogue pressure and temperature gauges, or may be computer-controlled with flow meters to electronically calibrate mix ratio, digital temperature and level sensors, and a full suite of statistical process control software. Add-ons to dispense equipment include nucleation or gas injection units, and third or fourth stream capability for adding pigments or metering in supplemental additive packages. Image:LowPressureMixHead600x800.png, A low-pressure mix head with calibration chamber installed, showing material supply and air actuator lines Image:LowPressureMixChamberComponents800x600.png, Low-pressure mix head components, including mix chambers, conical mixers, and mounting plates Image:LowPressure5GallonDayTanks800x600.png, 5-gallon (20-liter) material day tanks for supplying a low-pressure dispense unit


Tooling

Distinct from pour-in-place, bun and boardstock, and coating applications, the production of piece parts requires tooling to contain and form the reacting liquid. The choice of mold-making material is dependent on the expected number of uses to end-of-life (EOL), molding pressure, flexibility, and heat transfer characteristics. RTV silicone is used for tooling that has an EOL in the thousands of parts. It is typically used for molding rigid foam parts, where the ability to stretch and peel the mold around undercuts is needed. The heat transfer characteristic of RTV silicone tooling is poor. High-performance, flexible polyurethane elastomers are also used in this way. Epoxy, metal-filled epoxy, and metal-coated epoxy is used for tooling that has an EOL in the tens of thousands of parts. It is typically used for molding flexible foam cushions and seating, integral skin and microcellular foam padding, and shallow-draft RIM bezels and fascia. The heat transfer characteristic of epoxy tooling is fair; the heat transfer characteristic of metal-filled and metal-coated epoxy is good. Copper tubing can be incorporated into the body of the tool, allowing hot water to circulate and heat the mold surface. Aluminum is used for tooling that has an EOL in the hundreds of thousands of parts. It is typically used for molding microcellular foam gasketing and cast elastomer parts, and is milled or extruded into shape. Mirror-finish
stainless steel Stainless steel, also known as inox, corrosion-resistant steel (CRES), or rustless steel, is an iron-based alloy that contains chromium, making it resistant to rust and corrosion. Stainless steel's resistance to corrosion comes from its chromi ...
is used for tooling that imparts a glossy appearance to the finished part. The heat transfer characteristic of metal tooling is excellent. Finally, molded or milled
polypropylene Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications. It is produced via chain-growth polymerization from the monomer Propene, propylene. Polypropylene belongs to the group of polyolefin ...
is used to create low-volume tooling for molded gasket applications. Instead of many expensive metal molds, low-cost plastic tooling can be formed from a single metal master, which also allows greater design flexibility. The heat transfer characteristic of polypropylene tooling is poor, which must be taken into consideration during the formulation process.


Applications

In 2007, the global consumption of polyurethane raw materials was above 12 million metric tons, and the average annual growth rate was about 5%. Revenues generated with PUR on the global market are expected to rise to approximately US$75 billion by 2022. As they are such an important class of materials, research is constantly taking place and papers published.


Degradation and environmental fate


Effects of visible light

Polyurethanes, especially those made using
aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...
isocyanates, contain chromophores that interact with light. This is of particular interest in the area of polyurethane coatings, where
light Light, visible light, or visible radiation is electromagnetic radiation that can be visual perception, perceived by the human eye. Visible light spans the visible spectrum and is usually defined as having wavelengths in the range of 400– ...
stability is a critical factor and is the main reason that
aliphatic In organic chemistry, hydrocarbons ( compounds composed solely of carbon and hydrogen) are divided into two classes: aromatic compounds and aliphatic compounds (; G. ''aleiphar'', fat, oil). Aliphatic compounds can be saturated (in which all ...
isocyanates are used in making polyurethane coatings. When PU foam, which is made using aromatic isocyanates, is exposed to visible light, it discolors, turning from off-white to yellow to reddish brown. It has been generally accepted that apart from yellowing, visible light has little effect on foam properties. This is especially the case if the yellowing happens on the outer portions of a large foam, as the deterioration of properties in the outer portion has little effect on the overall bulk properties of the foam itself. It has been reported that exposure to visible light can affect the variability of some physical property test results. Higher-energy UV radiation promotes chemical reactions in foam, some of which are detrimental to the foam structure.


Hydrolysis and biodegradation

Polyurethanes may degrade due to
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
. This is a common problem with shoes left in a closet, and reacting with moisture in the air. Microbial degradation of polyurethane is believed to be due to the action of
esterase In biochemistry, an esterase is a class of enzyme that splits esters into an acid and an alcohol in a chemical reaction with water called hydrolysis (and as such, it is a type of hydrolase). A wide range of different esterases exist that differ ...
, urethanase,
hydrolase In biochemistry, hydrolases constitute a class of enzymes that commonly function as biochemical catalysts that use water to break a chemical bond: :\ce \quad \xrightarrowtext\quad \ce This typically results in dividing a larger molecule into s ...
and
protease A protease (also called a peptidase, proteinase, or proteolytic enzyme) is an enzyme that catalysis, catalyzes proteolysis, breaking down proteins into smaller polypeptides or single amino acids, and spurring the formation of new protein products ...
enzymes. The process is slow as most microbes have difficulty moving beyond the surface of the polymer. Susceptibility to fungi is higher due to their release of extracellular enzymes, which are better able to permeate the polymer matrix. Two species of the Ecuadorian fungus ''
Pestalotiopsis ''Pestalotiopsis'' is a genus of ascomycete fungi in the Sporocadaceae family. Taxonomy The genus was circumscription (taxonomy), circumscribed by René Leopold Alix Ghislain Jules Steyaert in Bull. Jard. Bot. Etat. vol.19 on page 300 in 1949. T ...
'' are capable of biodegrading polyurethane in aerobic and anaerobic conditions such as found at the bottom of
landfill A landfill is a site for the disposal of waste materials. It is the oldest and most common form of waste disposal, although the systematic burial of waste with daily, intermediate and final covers only began in the 1940s. In the past, waste was ...
s. Degradation of polyurethane items at museums has been reported. Polyester-type polyurethanes are more easily biodegraded by fungus than polyether-type.


See also

*
Botanol Botanol is a synthetic material, typically used as a floor covering, made from approximately 90% renewable raw materials including canola oil, castor oil and chalk. Botanol was formulated as an eco-friendly alternative to polyurethane. Backgrou ...
, a material with higher plant-based content *
Passive fire protection Passive fire protection (PFP) is components or systems of a building or structure that slows or impedes the spread of the effects of fire or smoke without system activation, and usually without movement. Examples of passive systems include floor- ...
* Penetrant (mechanical, electrical, or structural) * Polyaspartic * Polyurethane dispersion *
Thermoplastic polyurethanes Thermoplastic polyurethane (TPU) is any of the polyurethane polymers that are thermoplastic; that is, they become pliable when heated and harden when cooled. This is in contrast to most polyurethanes, which are thermosets, hardening irreversibly ...
* Thermoset polymer matrix


References


External links


Center for the Polyurethanes Industry
information for EH&S issues related to polyurethanes developments

Polymer Science Learning Center,
University of Southern Mississippi The University of Southern Mississippi (Southern Miss or USM) is a Public university, public research university with its main campus in Hattiesburg, Mississippi. It is accredited by the Southern Association of Colleges and Schools to award bac ...

Polyurethane Foam Association
Industry information, educational materials and resources related to flexible polyurethane foam
PU Europe: European PU insulation industry association
(formerly BING): European voice for the national trade associations representing the polyurethane insulation industry
ISOPA: European Diisocyanate & Polyol Producers Association
ISOPA represents the manufacturers in Europe of aromatic diisocyanates and polyols {{Authority control 1937 in Germany 1937 in science Adhesives Building insulation materials Coatings Elastomers Plastics Wood finishing materials German inventions of the Nazi period